EP2490791B1 - Verfahren zur co2-abscheidung mit carbonaten und biokatalysatoren - Google Patents

Verfahren zur co2-abscheidung mit carbonaten und biokatalysatoren Download PDF

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EP2490791B1
EP2490791B1 EP10805916.3A EP10805916A EP2490791B1 EP 2490791 B1 EP2490791 B1 EP 2490791B1 EP 10805916 A EP10805916 A EP 10805916A EP 2490791 B1 EP2490791 B1 EP 2490791B1
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absorption
solution
enzyme
carbonate
biocatalysts
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French (fr)
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EP2490791A4 (de
EP2490791A1 (de
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Sylvie Fradette
Julie Gingras
Jonathan Carley
Glenn R. Kelly
Olivera Ceperkovic
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Co2 Solutions Inc
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Co2 Solutions Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/88—Lyases (4.)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20494—Amino acids, their salts or derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B01D2252/602—Activators, promoting agents, catalytic agents or enzymes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/804—Enzymatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y402/00—Carbon-oxygen lyases (4.2)
    • C12Y402/01—Hydro-lyases (4.2.1)
    • C12Y402/01001—Carbonate dehydratase (4.2.1.1), i.e. carbonic anhydrase
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/59—Biological synthesis; Biological purification

Definitions

  • the present invention relates generally to CO 2 capture and more particularly to a process for CO 2 capture using carbonates and biocatalysts.
  • GHGs man-made greenhouse gas
  • the CCS process removes CO 2 from a CO 2 containing flue gas, enables production of a highly concentrated CO 2 gas stream which is compressed and transported to a sequestration site.
  • This site may be a depleted oil field or a saline aquifer.
  • Sequestration in ocean and mineral carbonation are two alternate ways to sequester that are in the research phase. Captured CO 2 can also be used for enhanced oil recovery.
  • This large cost for the capture portion has, to present, made large scale CCS unviable; based on data from the IPCC, for instance, for a 700 megawatt (MW) pulverized coal power plant that produces 4 million metric tons of CO 2 per year, the capital cost of conventional CO 2 capture equipment on a retrofit basis would be nearly $800 million and the annual operating cost and plant energy penalty would be nearly $240 million. As such, there is a need to reduce the costs of the process and develop new and innovative approaches to the problem.
  • MW megawatt
  • WO2008/072979 describes a method for capturing CO 2 from exhaust gas in an absorber, wherein the CO 2 containing gas is passed through an aqueous absorbent slurry that includes an inorganics alkali carbonate.
  • the predominant mechanism for CO 2 absorption is:
  • Another feature of carbonate based solutions is that, as CO 2 reacts with the compound, the product may form precipitates.
  • the presence of solids in the absorption solution enables the shift of the chemical reaction equilibria resulting in a constant CO 2 pressure when the loading of the solution increases.
  • Biocatalysts have also been used for CO 2 absorption purposes. More specifically, CO 2 transformation may be catalyzed by the enzyme carbonic anhydrase as follows:
  • the catalyzed turnover rate of this reaction may reach 1 x 10 6 molecules/second.
  • Carbonic anhydrase has been used as an absorption promoter in amine based solutions to increase the rate of CO 2 absorption. Indeed, particular focus has been made on amine solutions for use in conjunction with carbonic anhydrase in CO 2 capture processes.
  • One reason why amine solutions have been favoured is that they have relatively low ionic strength, which is a property viewed as significant for carbonic anhydrase hydration activity, since high ionic strength could be detrimental to the stability and function of the protein.
  • the present invention responds to the above mentioned need by providing a process for CO 2 capture using carbonates and biocatalysts.
  • the present invention provides a process for capturing CO 2 from a CO 2 -containing gas comprising: contacting the CO 2 -containing gas with an absorption mixture comprising water, biocatalysts and a carbonate compound to enable dissolution and transformation of CO 2 into bicarbonate and hydrogen ions, thereby producing a CO 2 -depleted gas and an ion-rich solution; and subjecting the ion-rich solution to desorption wherein the carbonate compound promotes release of the bicarbonate ions from the ion-rich solution producing a CO 2 gas stream and an ion-depleted solution, in accordance with claim 1.
  • the process includes removing the biocatalyst from the ion-rich solution prior to subjecting the ion-rich solution to the desorption.
  • the process includes removing the biocatalyst from the ion-rich solution after subjecting the ion-rich solution to the desorption.
  • the process includes recycling the ion-lean solution to form at least a part of the absorption mixture for re-contacting the CO 2 -containing gas.
  • the process includes adding an amount of biocatalyst into the ion-lean solution to convert the same into at least part of the absorption mixture for recycling to contact the CO 2 -containing gas.
  • the carbonate compound is selected and used in a sufficient amount in the absorption mixture such that the ion-rich solution contains bicarbonate precipitates.
  • the process includes removing the bicarbonate precipitates from the absorption mixture prior to subjecting the ion-rich solution to the desorption.
  • the bicarbonate precipitates remain in the ion-rich solution upon subjecting the ion-rich solution to the desorption, thereby converting into part of the CO 2 gas stream.
  • the bicarbonate precipitates may be composed of bicarbonate species comprising potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, or a mixture thereof.
  • the carbonate compound comprises potassium carbonate, sodium carbonate or ammonium carbonate, or a combination thereof.
  • the absorption mixture comprises an additional absorption compound.
  • the additional absorption compound comprises N-methyl N-secondary butyl glycine, diethylglycine, or dimethylglycine, or a combination thereof.
  • the process includes contacting the absorption mixture with the CO 2 -containing gas is performed in an absorption stage comprising at least one reactor selected from a packed tower, a vertical or horizontal spray scrubber, a fluidized bed reactor or a series of reactors comprising the same.
  • a sufficient level of CO 2 loading is provided in the absorption stage to promote the precipitation of bicarbonate precipitates.
  • the carbonate compound and biocatalysts are provided in concentrations to achieve a maximum range of relative CO 2 transfer rate, with respect to a CO 2 transfer rate without biocatalyst.
  • the carbonate compound is preferably provided in the absorption mixture in a concentration of at least about 0.1 M.
  • the carbonate compound may also be provided in the absorption mixture in a concentration at or below saturation thereof.
  • the carbonate compound may comprise potassium carbonate and be provided in the absorption mixture in a concentration up to the solubility limit at a temperature range between about 40°C and about 70°C.
  • the carbonate compound may comprise sodium carbonate and be provided in the absorption mixture in a concentration up to the solubility limit at a temperature range between about 40°C and about 70°C.
  • the biocatalyst is carbonic anhydrase.
  • the biocatalyst is provided free in the water; dissolved in the water; immobilized on the surface of supports that are mixed in the water and are flowable therewith; entrapped or immobilized by or in porous supports that are mixed in the water and are flowable therewith; as cross linked aggregates or crystals or a combination thereof.
  • the biocatalysts may preferably be supported by micro-particles that are carried in the water.
  • FIGS 1 and 2 respectively show two different embodiments of the process of the present invention.
  • Carbonate compounds promote the release of the bicarbonate ions from the water solvent during desorption.
  • the absorption step of the CO 2 capture process is improved due to the activation ability of the biocatalysts and the desorption step is rendered more efficient by virtue of the predominance of carbonate compounds. This improvement aids in enhancing the overall CO 2 capture process.
  • the carbonate compound is of the type and is added in sufficient quantities to promote precipitation of a bicarbonate species during absorption.
  • the process parameters may be controlled to further promote such precipitation.
  • the carbonates may be chosen such that the corresponding precipitates have characteristics making them easy to handle with the overall process, by allowing them to be suspended in the reaction solution, pumped, sedimented, etc., as the case may be.
  • the precipitates may be part of the ion-rich solution that is sent for desorption or treated separately for conversion into CO 2 gas. More particularly, the precipitates may be bicarbonate species, such as KHCO 3 , NaHCO 3 or NH 4 HCO 3 , and the carbonate compounds may be chosen to allow precipitation of such species.
  • the carbonate compounds also enable lower energy process parameters for desorption.
  • the particles when the enzymes are provided on or in particles flowing with the solution, the particles may be removed from the ion-rich solution before the ion-rich solution is fed into the desorption unit. Due to their nature and method of immobilisation on the particles, the biocatalysts may be more or less vulnerable to high temperatures. Thus, when desorption is operated at temperatures that could denature the given biocatalysts, the particles are preferably removed before desorption and recycled back into the absorption unit. The carbonates remain in the solution and enhance desorption. It may be preferred that the particles are provided such that they may be easily separated from the bicarbonate precipitate, if need be.
  • the desorption when the biocatalysts are allowed to be present during desorption, the desorption is preferably operated at pressures and temperatures that are tolerable for the given biocatalyst so that the biocatalysts retain their activity, increase desorption rate by catalyzing bicarbonate ion dehydration and can be recycled back into the absorption unit. Desorption may be managed in such cases by reducing the pressure rather than raising the temperature.
  • the biocatalysts in the absorption mixture are the enzymes carbonic anhydrase.
  • the biocatalysts include carbonic anhydrase to enhance performance of absorption solutions for CO2 capture.
  • the enzyme may be provided directly as part of a formulation or may be provided in a reactor to react with incoming solutions and gases.
  • the enzyme may be fixed ta a solid non-porous packing material, on or in a porous packing material, on or in particles flowing with the absorption solution within a packed tower or another type of reactor.
  • the carbonic anhydrase may be in a free or soluble state in the formulation or immobilized on particles within the formulation.
  • enzyme used in a free state may be in a pure form or may be in a mixture including impurities or additives such as other proteins, salts and other molecules coming from the enzyme production process.
  • Immobilized enzyme free flowing in the absorption solution could be entrapped inside or fixed to a porous coating material that is provided around a support that is porous or non-porous.
  • the enzymes may be immobilised directly onto the surface of a support (porous or non porous) or may be present as "cross linked enzymes aggregates" (CLEA) or “cross linked enzymes crystals” (CLEC).
  • CLA cross linked enzymes aggregates
  • CLEC cross linked enzymes crystals
  • the CLEA may or may not have a 'support' or 'core' made of another material which may or may not be magnetic.
  • CLEC comprise enzyme crystals and cross linking agent and may also be associated with a 'support' or 'core' made of another material.
  • a support it may be made of polymer, ceramic, metal(s), silica, solgel, chitosan, cellulose, magnetic particles and/or other materials known in the art to be suitable for immobilization or enzyme support.
  • the enzymes are immobilised or provided on particles, such as micro-particles, the particles are preferably sized and provided in a particle concentration such that they are pumpable with the absorption solution.
  • Biocatalysts may also be provided both fixed within the reactor (on a packing material, for example) and flowing with the formulation (as free enzymes, on particles and/or as CLEA or CLEC), and may be the same or different biocatalysts.
  • One of the ways carbonic anhydrase enhances performance of carbonate solutions is by reacting with dissolved CO 2 and maintaining a maximum CO 2 concentration gradient between gas and liquid phases and then maximizing CO 2 transfer rate from the gas phase to the solution.
  • the carbonate compounds may also enable the precipitation of precipitates to further improve the CO 2 concentration gradient between gas and liquid phases and thus further increasing CO 2 transfer rate.
  • the biocatalysts may be provided using means depending on the concentration and type of carbonate compound, the process operating parameters, and other factors. For instance, when a high concentration of carbonate compounds Is provided, the enzymes may be immobilised on a support to reduce the possibility of deactivation by the carbonates. In some embodiments, the biocatalysts may be advantageously immobilised in a micro-porous structure (which may be a support or a material coating a support) allowing access of CO 2 while protecting it against high concentrations of carbonate compounds.
  • the carbonate compounds used in the formulation may include potassium carbonate, sodium carbonate, promoted potassium carbonate solutions and promoted sodium carbonate solutions or mixtures thereof.
  • the biocatalysts which may be provided on or in particles, are added to the lean absorption solution in a mixing chamber (E-4).
  • the lean absorption solution refers to the absorption solution characterized by a low concentration of the species to be absorbed. This solution is either fresh solution or comes from the mineral carbonation process or the CO 2 desorption process (10).
  • the absorption solution with biocatalysts (11) is then fed to the top of a packed column (E-1) with a pump (E-7).
  • the packing material (9) may be made of conventional material like polymers, metal and ceramic. The geometry of the packing may be chosen from what is commercially available.
  • the packing preferably has limited upward facing concavities to avoid the accumulation of micro-particles therein.
  • the micro-particles and packing are chosen so that the micro-particles can flow through the reactor without clogging.
  • the biocatalysts can be provided on the packing rather than in the absorption mixture.
  • the absorption mixture with biocatalysts that may be supported by particles and carbonate solution flows on, through, and/or around the packing material (9) from the top of the column to the bottom.
  • the absorption solution becomes richer in the compound that is being absorbed, which is CO 2 .
  • Biocatalysts present near the gas-liquid interface, enhance CO 2 absorption by immediately reacting with CO 2 to produce bicarbonate ions and protons and thus maximizing the CO 2 concentration gradient across the interface.
  • the rich absorption mixture containing the biocatalysts and bicarbonates ions (13) are pumped (E-5) to a particle separation unit (E-3).
  • Rich absorption solution refers to the absorption mixture characterized by a concentration of absorbed compound which is higher than that of the lean solution.
  • the separation unit may comprise a filtration unit (such as a tangential filtration unit), a centrifuge, a cyclone, a sedimentation tank or a magnetic separator and any other units or equipments known for particle or solid separation.
  • the separation unit also enables a certain quantity of solution to be retained with the biocatalytic micro-particles so they do not dry out which can denature the biocatalysts.
  • the quantity of retained solution enables the biocatalytic micro-particles to be pumped to a storage unit or directly back to a mixing chamber (E-4) for addition into the absorption unit.
  • the biocatalysts with retained solution may be gravity fed into the mixing chamber (E-4), which may be enabled by performing separation above the mixing unit, for example. The separation may be conducted in continuous or in batch mode, and may be managed to ensure the proper amount of solution is retained to ensure enzyme activity. It may also be preferred that the biocatalytic micro-particles are provided such that they may be easily separated from any solid precipitates (e.g. bicarbonate precipitates) that may be entrained in the ion-rich solution, if need be.
  • any solid precipitates e.g. bicarbonate precipitates
  • the absorption mixture without biocatalytic micro-particles (15) is then pumped (E-9) to a regeneration stage, which includes CO 2 desorption (10).
  • Biocatalytic micro-particles (16) are mixed with the CO 2 lean absorption solution. This suspension is then fed once again to the absorption column (E-1).
  • the absorption unit is coupled to a desorption unit as shown in further detail in Figure 2 .
  • the absorption solution rich in CO 2 without biocatalytic micro-particles (15) is pumped (E-9) through a heat exchanger where it is heated and then sent on to the desorption column (E-11).
  • the solution is further heated in order that the CO 2 is released from the solution in a gaseous state. Because of relatively high temperature used during desorption, water also vaporizes. Part of the absorption solution is directed toward a reboiler where it is heated to a temperature enabling CO 2 desorption. Gaseous CO 2 together with water vapour are cooled down, water condenses and is fed back to the desorption unit.
  • Dry gaseous CO 2 is then directed toward a compression and transportation process for further processing.
  • the liquid phase, containing less CO 2 , and referred to as the lean absorption solution (17) is then pumped (E-14) to the heat exchanger to be cooled down and fed to the mixing chamber (E-4).
  • the temperature of the lean absorption solution (17) should be low enough not to denature the enzyme if present.
  • the biocatalysts might also help in improving the rate of CO 2 dehydration and thus increasing CO 2 desorption rate resulting in smaller desorption equipment.
  • the biocatalysts may have an impact in the absorption unit by increasing the CO 2 absorption rate but also in the desorption unit since an enzyme such as carbonic anhydrase can increase the rate of bicarbonate ion transformation into CO 2 (which is one of the reactions that would take place in the desorption unit).
  • the removal unit (E-3) would be required to remove deactivated biocatalysts and unit E-4 to add fresh biocatalysts.
  • a separation unit such as a filter between (E-11) and the reboiler to avoid flow of biocatalysts through the reboiler and their contact with very high temperatures (depending on the thermoresistance of the enzymes).
  • the mixing chamber (E-4) preferably comprises an inlet for receiving recycled biocatalysts from the separation unit (E-3) and also an inlet/outlet for both removing a fraction of deactivated biocatalysts and replacing them with new fresh biocatalyst, thereby refurbishing the overall batch of biocatalysts in the system.
  • biocatalysts are filtered, centrifuged, cycloned, sedimented or separated magnetically in a first separation unit (according to their above-mentioned support system) and other small particles such as bicarbonate precipitates can be separated in a preceding or subsequent separation unit.
  • the biocatalysts are used in conjunction with additional absorption compounds in the absorption mixture, which include N-methyl N-secondary butyl glycine, diethylglycine, dimethylglycine, and/or mixtures thereof.
  • Absorption compounds are added to the solution to aid in the CO 2 absorption and to combine with the catalytic effects of the carbonic anhydrase. Due to the structure or high concentration of some absorption compounds, the activity or longevity of the carbonic anhydrase can be threatened. For instance, free enzymes may be more vulnerable to denaturing caused by an absorption compound with high ionic strength. Immobilising the carbonic anhydrase can mitigate the negative effects of such absorption compounds. By providing enzymes immobilsed on a support material, such as for example on micro-particles, the process can yield high CO 2 transfer rates in the presence of absorption compounds while mitigating the negative effects such compounds could otherwise have on free enzymes.
  • the absorption solution is an aqueous solution of potassium carbonate (K 2 CO 3 ) 20% (w/w) (equivalent to 1.45 M). This, absorption solution is contacted counter-currently with a gas phase with a CO 2 concentration of 130,000 ppm. Liquid flow rate was 0.6 g/min and gas flow rate was 60 g/min corresponding to L/G of 10 (g/g). Gas and absorption solution were at room temperature. Operating pressure of the absorber was set at 0.1 bar (1.4 psig). The column has a 7.5 cm diameter and a 50 cm height. Packing material is polymeric Raschig rings 0.6 cm (0.25 inch).
  • the absorption solution is an aqueous solution of sodium carbonate (Na 2 Co 3 ) 0.5M. This absorption solution is contacted counter-currently with a gas phase with a CO 2 concentration of 130,000 ppm. Liquid flow rate was 0.65 g/min and gas flow rate was 65 g/min corresponding to L/G of 10 (g/g). Gas and absorption solution were at room temperature. Operating pressure of the absorber was set at 0.1 bar (1.4 psig). The column has a 7.5 cm diameter and a 50 cm height. Packing material is polymeric Raschig rings 0.6 cm (0.25 inch). Three tests were performed: the first with no biocatalyst, the second with carbonic anhydrase immobilized to packing support and the third using carbonic anhydrase free in solution at a concentration of 0.5 g per liter of solution.
  • the absorption solution is an aqueous solution of ammonium carbonate (NH 4 )CO 3 /(NH 4 )OH 8M (ammonium).
  • This absorption solution is contacted counter-currrently with a gas phase with a CO 2 concentration of 130 000 ppm.
  • Liquid flow rate was 0.25 g/min and gas flow rate was 63 g/min corresponding to L/G of 4 (g/g).
  • Gas and absorption solution were at room temperature.
  • Operating pressure of the absorber was set at 0.1 bar (1.4 psig).
  • the column has a 7.5 cm diameter and a 50 cm height. Packing material is polymeric Raschig rings 0.6 cm (0.25 inch). Two tests were performed: the first with no biocatalyst, and the second using carbonic anhydrase immobilized to packing.
  • a known pressure of pure CO 2 is applied to the solution, the pressure corresponds to the CO 2 partial pressure that can be found in an industrial post-combustion flue gas.
  • initial CO 2 pressure is 200 mbar.
  • the pressure decrease is monitored and used to calculate CO 2 transfer rate in the absorption.
  • Results are expressed as a ratio of the CO 2 transfer rate with enzyme to the CO 2 transfer rate in the absence of the enzyme (see Figure 3 ). Results clearly indicate that adding enzyme to the 1.45 M K 2 CO 3 solution brings an important benefit for all tested conditions. Impact is more important when the enzyme concentration is higher. Results also indicate that the CO 2 loading of the solution has an impact on the improvement brought by the enzyme.
  • the impact obtained in stirred cells is similar to that obtained in a packed column (see Example 2). It is assumed, as for other system reported in literature, that we could predict from stirred cell results the impact of the enzyme in a packed column.
  • Tests were conducted in a hydration cell at an enzyme concentration of 500 mg/L in K 2 CO 3 solutions with concentrations of 0.5, 1 and 1.45 M at a temperature of 20°C.
  • Enzyme used is human carbonic anhydrase type II.
  • Initial CO 2 loading is 0 mol CO 2 /mol K 2 CO 3 .
  • the hydration cell and testing methods are different from the one described in Example 4 in that a continuous flow of pure CO 2 is flushed in this cell at a pressure of 1 atma, at the surface of the liquid phase (with or without enzyme) and pH change of the solution is monitored. Changes in pH are correlated to changes in inorganic carbon concentration which are used to calculate CO 2 transfer rates.
  • Results are expressed as a ratio of CO 2 transfer rate with enzyme to CO 2 transfer rate in the absence of the enzyme (see Figure 4 ). It is important to note, that as such, as the hydration cell is used for more rapid, indicative testing of enzyme catalytic activity, the corresponding results are not viewed to be as precise as those obtained in Example 4. This fact generally explains any variation in observed results between the two testing systems under similar conditions. Results clearly indicate that enzyme brings an important benefit for all tested K 2 CO 3 solutions.
  • Tests were conducted in a hydration cell at an enzyme concentration of 500 mg/L in Na 2 CO 3 solutions with concentrations of 0.1, 0.25 and 0.5 M at a temperature of 20°C. Method is described in Example 5. Enzyme used is HCAII. Initial CO 2 loading is 0 mol CO 2 /mol Na 2 CO 3 . Results are expressed as a ratio of CO 2 transfer rate with enzyme to CO 2 transfer rate in the absence of the enzyme (see Figure 5 ). Results clearly indicate that enzyme brings an important benefit for all tested Na 2 CO 3 solutions.
  • the biocatalytic particles are mixed in the lean absorption solution in a mixing chamber (E-4).
  • the biocatalytic particles have a size enabling their flow on, through, and/or around the packing of the packed column without clogging.
  • the lean absorption solution refers to the absorption solution characterized by a low concentration of the species to be absorbed. This solution is either fresh solution or comes from the CO 2 desorption process (1).
  • the absorption solution with biocatalytic particles (11) is then fed to the top of a packed column (E-1) with a pump (E-7).
  • the packing material (9) may be made of conventional material like polymers, metal and ceramic.
  • the geometry of the packing may be chosen from what is commercially available.
  • the packing preferably is chosen to have geometry or packing arrangement, to facilitate the flow of small particles present or generated in the absorption solution. Examples of packing are: Pall rings, Raschig rings, Flexipak, Intalox, etc.
  • a CO 2 containing gas (12) is fed to the packed column (E-1) and flows through the packing (9) from the bottom to the top of the column.
  • the absorption solution and biocatalytic particles flow through the packing material (9) from the top of the column to the bottom.
  • the absorption solution and biocatalytic particles As the absorption solution and biocatalytic particles flow on, through, and/or around the packing, the absorption solution becomes richer in the compound that is being absorbed, in this case CO 2 .
  • Biocatalytic particles present near the gas-liquid interface, enhance CO 2 absorption by immediately reacting with CO 2 to produce bicarbonate ions and protons and thus maximizing the CO 2 concentration gradient across the gas-liquid interface.
  • the rich absorption solution and biocatalytic particles (13) are pumped (E-5) to a particle separation unit (E-3).
  • Rich absorption solution refers to the absorption solution characterized by a concentration of absorbed compound which is higher than that of the lean solution.
  • the separation unit may consist of a filtration unit, a centrifuge, a sedimentation tank, magnetic separator and/or any other units or equipment known for particles or solid separation.
  • the absorption solution without particles (15) is then pumped (E-9) to another unit which may be a CO 2 desorption unit (10).
  • Biocatalytic particles (16) are pumped (E-6) to a mixing chamber (E-4) where they are mixed with the CO 2 lean absorption solution.
  • the mixing chamber may be equipped with an impeller or another device which function is to assure that biocatalytic particles are mixed and/or suspended in the absorption solution which is then pumped (E-7) once again to the absorption column (E-1).
  • the absorption unit is coupled to a desorption unit as shown in further detail in Figure 2 .
  • the absorption solution rich in CO 2 with or without biocatalytic particles (15) is pumped (E-9) to the desorption column (E-11) operated at a lower pressure than the absorption.
  • the desorption unit the decrease in pressure and/or increase in temperature causes that the CO 2 is released from the solution in a gaseous state. Because of relatively low pressure used during desorption, water also vaporizes. Gaseous CO 2 together with water vapour are cooled down, water condenses and is fed back to the desorption unit. Dry gaseous CO 2 is then directed toward a compression and transportation process for further processing.
  • the liquid phase, containing less CO 2 and referred to as the lean absorption solution (17) is then pumped (E-14) to the mixing chamber (E-4).
  • the rate of desorption is increased, the energy required for desorption may be reduced and more enzyme activity can be maintained for recycling back to the absorption unit.
  • the absorption solution rich in CO 2 without biocatalytic particles (15) is pumped (E-9) through a heat exchanger where it is heated and then to the desorption column (E-11).
  • the solution is further heated in order that the CO 2 is released from the solution in a gaseous,state.
  • water also vaporizes.
  • Part of the absorption solution is directed toward a reboiler where it is heated to a temperature enabling CO 2 desorption. Gaseous CO 2 together with water vapour are cooled down, water condenses and is fed back to the desorption unit. Dry gaseous CO 2 is then directed toward a compression and transportation process for further processing.
  • the liquid phase, containing less CO 2 , and referred to as the lean absorption solution (17) is then pumped (E-14) to the heat exchanger to be cooled down and fed to the mixing chamber (E-4).
  • the temperature of the lean absorption solution (17) should be low enough not to denature the enzyme.
  • amino acids used in the absorption solution may also be amino acids used in the absorption solution.
  • the amino acids may include potassium salt of amino acids.
  • the amino acids may be for instance glycine, proline, arginine, histidine, lysine, aspartic acid, glutamic acid, methionine, serine, threonine, glutamine, cysteine, asparagine, valine, leucine, isoleucine, alanine, tyrosine, tryptophan, phenylalanine, and derivatives such as taurine, N,cyclohexyl 1,3-propanediamine, N-secondary butyl glycine, N-methyl N-secondary butyl glycine,, diethylglycine, dimethylglycine, sarcosine, methyl taurine, methyl- ⁇ -aminopropionic acid, N-( ⁇ -ethoxy)taurine, N- ⁇ -aminoethyl)tau
  • the amino acid may act as an absorption promoter to further increase the performance of the formulation, process and system.
  • the amino acid promoter is used in conjunction with the biocatalyst immobilised on a packing in a packed-tower absorption reactor.
  • the absorption and desorption reactors may be various different types depending on the particular process to be performed.
  • the reactors types may be chosen depending on the presence of free-flowing biocatalysts or micro-particles with immobilised biocatalysts, the degree of precipitation of carbonate species, pressure, temperature, flue gas conditions and properties, etc.
  • the absorption reactor for example, may be a packed-tower, vertical or horizontal spray scrubber, or fluidised bed reactor.
  • the absorption solution is an aqueous solution of potassium carbonate (K 2 CO 3 ) 1.45 M. This absorption solution is contacted counter-currently with a gas phase with a CO 2 concentration of 130,000 ppm. Liquid flow rate was 0.60 g/min and gas flow rate was 60 g/min corresponding to L/G of 10 (g/g). Gas and absorption solution were at room temperature. Operating pressure of the absorber was set at 0.1 bar (1.4 psig). The column has a 7,5 cm diameter and a 50 cm height. Packing material is polymeric Raschig rings 0.6 cm (0.25 inch).
  • This example provides data to demonstrate that enzyme immobilization increases enzyme stability. Data are shown for enzyme immobilized on nylon micro-particles. To evaluate the impact of immobilization on enzyme stability, the stability of immobilized enzymes was evaluated and compared to the stability of the same enzyme in a soluble form.
  • Non-limiting example of nylon micro-particles are non-limiting examples of nylon micro-particles.
  • Micro-particles were prepared through the following non-optimized steps:
  • results show that free enzyme loses all activity with 10 days, whereas micro-particles still retain 40% residual activity after 56 days. From this result, it is clear that immobilization increases enzyme stability under these conditions.
  • Figure 8 illustrates the results.
  • the biocatalyst is provided to enable increased stability around or above the stability increase illustrated in the examples. These results show the potential of immobilization to increase the stability of carbonic anhydrase at higher temperature conditions that are found in a CO 2 capture process. These results were obtained in MDEA 2M at 40°C and it is expected that a similar increase in stability will also be present in carbonate solutions.
  • the biocatalyst is provided to enable increased stability around or above the stability increase illustrated in the examples.
  • the absorption and desorption units that may be used with embodiments of the present invention can be different types depending on various parameters and operating conditions.
  • the reactors types may be chosen depending on the presence of free biocatalysts, biocatalytic micro-particles, biocatalytic fixed packing, etc.
  • the units may be, for example, in the form of a packed reactor, spray reactor, fluidised bed reactor, etc., may have various configurations such as vertical, horizontal, etc., and the overall system may use multiple units in parallel or in series, as the case may be.

Claims (12)

  1. Verfahren zum Abscheiden von CO2 aus einem CO2-haltigen Gas, umfassend:
    Inkontaktbringen des CO2-haltigen Gases mit einem Absorptionsgemisch umfassend Wasser, Biokatalysatoren und eine Carbonatverbindung, um Auflösung und Transformation von CO2 zu Bicarbonat und Wasserstoffionen zu ermöglichen, wobei ein an CO2-abgereichertes Gas und eine ionenreiche Lösung hergestellt werden,
    und
    Unterziehen der ionenreichen Lösung einer Desorption, wobei die Carbonatverbindung in einer ausreichenden Menge vorliegt, um Freisetzung der Bicarbonationen aus der ionenreichen Lösung zu fördern, was einen CO2-Gasstrom und eine an Ionen abgereicherte Lösung herstellt;
    wobei die Carbonatverbindung Kaliumcarbonat, Natriumcarbonat oder Ammoniumcarbonat, oder eine Kombination davon umfasst;
    wobei das Absorptionsgemisch eine zusätzliche Absorptionsverbindung umfasst, und wobei die zusätzliche Absorptionsverbindung N-Methyl-N-sekundäres Butylglycin, Diethylglycin oder Dimethylglycin, oder eine Kombination davon umfasst; und
    wobei der Biokatalysator Carboanhydrase ist.
  2. Verfahren nach Anspruch 1, umfassend Recycling der an Ionen abgereicherten Lösung, um mindestens einen Teil des Absorptionsgemisches zum Wiederinkontaktbringen des CO2-haltigen Gases zu bilden.
  3. Verfahren nach Anspruch 2, umfassend Zufügen einer Menge an Biokatalysator in die an Ionen abgereicherte Lösung, um diese in mindestens einen Teil des Absorptionsgemisches zum Recycling umzuwandeln, um das CO2-haltige Gas in Kontakt zu bringen.
  4. Verfahren nach einem beliebigen der Ansprüche 1 bis 3, wobei die zusätzliche Absorptionsverbindung Diethylglycin ist.
  5. Verfahren nach einem beliebigen der Ansprüche 1 bis 3, wobei die zusätzliche Absorptionsverbindung Dimethylglycin ist.
  6. Verfahren nach einem beliebigen der Ansprüche 1 bis 3, wobei die zusätzliche Absorptionsverbindung N-Methyl-N-sekundäres Butylglycin ist.
  7. Verfahren nach einem beliebigen der Ansprüche 1 bis 6, wobei ein ausreichender Spiegel an CO2-Beladung im Absorptionsstadium bereitgestellt wird, um die Fällung von Bicarbonatpräzipitaten zu fördern.
  8. Verfahren nach einem beliebigen der Ansprüche 1 bis 7, wobei die Carbonatverbindung und die Biokatalysatoren in Konzentrationen bereitgestellt werden, um einen maximalen Bereich relativer CO2-Transfergeschwindigkeit zu erreichen, bezogen auf eine CO2-Transfergeschwindigkeit ohne Biokatalysator.
  9. Verfahren nach einem beliebigen der Ansprüche 1 bis 8, wobei die Carbonatverbindung im Absorptionsgemisch in einer Konzentration bei oder unterhalb der Sättigung davon bereitgestellt wird.
  10. Verfahren nach einem beliebigen der Ansprüche 1 bis 9, wobei das Kaliumcarbonat im Absorptionsgemisch in einer Konzentration bis zur Löslichkeitsgrenze bei einem Temperaturbereich zwischen 40°C und 70°C bereitgestellt wird, oder wobei das Natriumcarbonat im Absorptionsgemisch in einer Konzentration bis zur Löslichkeitsgrenze bei einem Temperaturbereich zwischen 40°C und 70°C bereitgestellt wird.
  11. Verfahren nach einem beliebigen der Ansprüche 1 bis 10, wobei der Biokatalysator frei im Wasser; gelöst im Wasser; immobilisiert an der Oberfläche von Trägern, die im Wasser gemischt und darin fließfähig sind; eingeschlossen oder immobilisiert durch oder in poröse(n) Träger(n), die im Wasser gemischt und darin fließfähig sind; als vernetzte Aggregate oder Kristalle; oder eine Kombination davon bereitgestellt wird.
  12. Verfahren nach einem beliebigen der Ansprüche 1 bis 10, wobei der Biokatalysator immobilisiert an der Oberfläche von Trägern, die im Wasser gemischt und darin fließfähig sind; eingeschlossen oder immobilisiert durch oder in poröse(n) Träger(n), die im Wasser gemischt und darin fließfähig sind; oder eine Kombination davon bereitgestellt wird.
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US8722391B2 (en) 2014-05-13
US9044709B2 (en) 2015-06-02
CA2769772A1 (en) 2011-02-10
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US9533258B2 (en) 2017-01-03
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US10226733B2 (en) 2019-03-12
US20120129246A1 (en) 2012-05-24
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WO2011014957A8 (en) 2011-03-17
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